Thermally stable Terbium(II) and Dysprosium(II) Bis-Amidinate Single-Molecule Magnets

20 July 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The thermostable four-coordinate divalent lanthanide (Ln) bis-amidinate complexes [Ln(Piso)2] (Ln = Tb, Dy; Piso = {(NDipp)2CtBu}, Dipp = C6H3iPr2-2,6) were prepared by the reduction of parent five-coordinate Ln(III) precursors [Ln(Piso)2I] (Ln = Tb, Dy) with KC8; halide abstraction of [Ln(Piso)2I] with [H(SiEt3)2][B(C6F5)] gave the respective Ln(III) complexes [Ln(Piso)2][B(C6F5)]. All complexes were characterized by single crystal and powder XRD, SQUID magnetometry UV-vis-NIR, ATR-IR, NMR and EPR spectroscopy, and ab initio CASSCF-SO calculations. These data consistently show that [Ln(Piso)2] formally exhibit Ln(II) centers with 4fn5dz21 (Ln = Tb, n = 8; Dy, n = 9) valence electron configurations. We show that simple assignments of the f-d coupling to either L−S or J−s schemes is an oversimplification, especially in the presence of significant crystal field splitting. The coordination geometry of [Ln(Piso)2] is intermediate between square planar and tetrahedral. Projecting from the quaternary carbon atoms of the CN2 ligand backbones shows near-linear C···Ln···C arrangements. This results in strong axial ligand fields to give effective energy barriers to magnetic relaxation of 1920(91) K for the Tb(II) analog and 1964(48) K for Dy(II), the highest values observed to date for any mononuclear Ln(II) single-molecule magnet (SMM).


divalent lanthanide
single-molecule magnet

Supplementary materials

supporting information
Additional experimental details for physical and computational data associated with this manuscript


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